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CN114807677A - Tin alloy and preparation method thereof - Google Patents

Tin alloy and preparation method thereof Download PDF

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Publication number
CN114807677A
CN114807677A CN202110561026.3A CN202110561026A CN114807677A CN 114807677 A CN114807677 A CN 114807677A CN 202110561026 A CN202110561026 A CN 202110561026A CN 114807677 A CN114807677 A CN 114807677A
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Prior art keywords
tin
tin alloy
germanium
cobalt
yttrium
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CN202110561026.3A
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CN114807677B (en
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罗登俊
陈钦
张阳
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Eunow Electronic Technology Co ltd Suzhou
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Eunow Electronic Technology Co ltd Suzhou
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C13/00Alloys based on tin
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01RELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R43/00Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
    • H01R43/02Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors for soldered or welded connections

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Conductive Materials (AREA)
  • Coating With Molten Metal (AREA)

Abstract

The invention belongs to the technical field of alloy materials, and particularly relates to a tin alloy and a preparation method thereof. A tin alloy is prepared from the following raw materials: at least three of copper, tin, germanium, nickel, cobalt and yttrium. The tin alloy prepared by the method can work at 380-430 ℃, and good pin tin plating and enameled wire welding are realized; the tin alloy prepared by the invention has clean enameled wire leather membrane residue in the enameled wire welding process and can not be attached to a welding spot; the tin alloy prepared by the invention has better high temperature resistance and oxidation resistance, and avoids the oxidation phenomenon possibly appearing on the surface of tin in the using process.

Description

Tin alloy and preparation method thereof
Technical Field
The invention belongs to the technical field of alloy materials, and particularly relates to a tin alloy and a preparation method thereof.
Background
In the welding work of the joints of the transformer enameled wires, a higher welding temperature is needed for removing the enameled wire leather membrane, but the enameled wire copper material is easily and seriously corroded at high temperature to cause failure, and the enameled wire leather membrane is easily coated on the surface of a welding spot to cause pollution.
Meanwhile, when the transformer pin is pulled away from the molten tin liquid surface in tin immersion, a pull tip is easy to occur, the appearance consistency of the pin is damaged, and adverse effects are caused on the joint welding work of the transformer enameled wire.
In order to avoid the pollution caused by the coating of the enameled wire covering the surface of the welding spot in the tin immersion welding process and the defect that the welding spot is easy to form a sharp tin point, the method still faces an important test and challenge.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present invention provides a tin alloy, which is prepared from the following raw materials: at least three of copper, tin, germanium, nickel, cobalt and yttrium.
As a preferred technical scheme, the preparation raw materials comprise copper, tin, germanium, cobalt and yttrium.
As a preferred technical scheme, the preparation raw materials comprise the following components in percentage by weight: 3 to 6 percent of copper, 0.15 to 0.3 percent of nickel, 0.001 to 0.075 percent of germanium, 0.001 to 0.01 percent of cobalt, 0.0005 to 0.005 percent of yttrium, and the balance of tin. As a preferred technical scheme, the preparation raw materials comprise the following components in percentage by weight: 3-5% of copper, 0.18-0.25% of nickel, 0.005-0.05% of germanium, 0.005-0.008% of cobalt, 0.0005-0.001% of yttrium and the balance of tin.
As a preferable technical proposal, the sum of the weight percentages of the cobalt and the yttrium is less than 0.06 percent.
As a preferable technical proposal, the sum of the weight percentages of the germanium and the cobalt is less than 0.06 percent.
As a preferable technical scheme, the sum of the weight percentages of the germanium and the yttrium is less than 0.06 percent.
As a preferable technical proposal, the sum of the weight percentages of the germanium, the cobalt and the yttrium is less than or equal to 0.06 percent.
The second aspect of the present invention provides a method for preparing a tin alloy, comprising the steps of:
1) preparing materials according to the mass percentage of the raw materials;
2) and (3) mixing the raw materials prepared in the step (1) to obtain a metal mixture, and then melting and homogenizing in a melting furnace to obtain the alloy.
In a third aspect of the invention, an enameled wire is provided, which is made of a tin alloy.
Has the advantages that: the tin alloy prepared by the invention has the following advantages:
1. the tin alloy prepared by the method can work at the temperature of 380-430 ℃, and good pin tin plating and enameled wire welding are realized;
2. the tin alloy prepared by the invention has clean enameled wire leather membrane residue in the enameled wire welding process and can not be attached to a welding spot;
3. the tin alloy prepared by the invention has smooth and flat pin coating in the using process, and the defect of tip pulling is avoided;
4. the tin alloy prepared by the invention has better high temperature resistance and oxidation resistance, and avoids the oxidation phenomenon possibly appearing on the surface of tin in the using process.
Detailed Description
The invention will be further understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
As used herein, a feature that is not limited to a single plural form is also intended to include plural forms of the feature unless the context clearly indicates otherwise. It will be further understood that the term "prepared from …," as used herein, is synonymous with "comprising," including, "comprising," "having," "including," and/or "containing," when used in this specification means that the recited composition, step, method, article, or device is present, but does not preclude the presence or addition of one or more other compositions, steps, methods, articles, or devices. Furthermore, the use of "preferred," "preferably," "more preferred," etc., when describing embodiments of the present application, is meant to refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to solve the above problems, a first aspect of the present invention provides a tin alloy, which is prepared from the following raw materials: at least three of copper, tin, germanium, nickel, cobalt and yttrium.
In some preferred embodiments, the preparation feedstock comprises copper, tin, germanium, cobalt, yttrium.
In some preferred embodiments, the preparation raw materials comprise, in weight percent: 3 to 6 percent of copper, 0.15 to 0.3 percent of nickel, 0.001 to 0.075 percent of germanium, 0.001 to 0.01 percent of cobalt, 0.0005 to 0.005 percent of yttrium, and the balance of tin.
In some preferred embodiments, the preparation raw materials comprise, in weight percent: 3 to 6 percent of copper, 0.15 to 0.25 percent of nickel, 0.001 to 0.06 percent of germanium, 0.005 to 0.008 percent of cobalt, 0.005 to 0.001 percent of yttrium, and the balance of tin.
In some preferred embodiments, the preparation raw materials comprise, in weight percent: 3-5% of copper, 0.18-0.25% of nickel, 0.005-0.05% of germanium, 0.005-0.008% of cobalt, 0.0005-0.001% of yttrium and the balance of tin.
In the experimental process, the inventor finds that the addition of germanium has an important influence on the effect of the prepared tin alloy in the using process. When the weight percentage of the germanium is 0.005-0.05%, the phenomenon of pin tip pulling in the welding process can be avoided, the inventor speculates that the use temperature of the tin alloy can be changed along with the addition of a certain content of germanium, the fluidity of tin is ensured in the use process, the phenomenon of over-low temperature possibly occurring in tin climbing is avoided, and the phenomenon of pin tip pulling is avoided.
The inventor finds that germanium is not added in the preparation process of the tin alloy in the experimental process, so that not only is a serious pin-pointing phenomenon caused, which affects the use of the tin alloy in an enameled wire, but also the use temperature of the tin alloy is greatly reduced, and the application value of the tin alloy is reduced.
In some preferred embodiments, the preparation raw materials comprise, in weight percent: 4.5% of copper, 0.2% of nickel, 0.04% of germanium, 0.006% of cobalt, 0.008% of yttrium and the balance of tin.
In some preferred embodiments, the preparation raw materials comprise, in weight percent: 5% of copper, 0.2% of nickel, 0.04% of germanium, 0.006% of cobalt, 0.008% of yttrium and the balance of tin.
The inventor researches and discovers through a large number of creative experiments that the copper content has an important influence on the prepared tin alloy in the process of welding the enameled wire. In the system, a compact and internal defect-free integral structure can be formed through the synergistic effect between copper and nickel, tin, germanium, cobalt and yttrium metals, under the condition, the diffusion of copper elements into a matrix is slowed down, the high-temperature resistance and the mechanical impact performance of tin alloy are improved, the possibility of using the tin alloy at 380-430 ℃ is ensured, good pin tinning and enameled wire welding are realized, a film of the enameled wire cannot be attached to a welding spot, and the enameled wire does not become thin and has no sharp phenomenon.
Meanwhile, the inventor finds that the reduction of the weight of copper causes the high temperature resistance of the tin alloy to be greatly reduced, and when the content of copper is 2%, a severe corrosion phenomenon occurs when a transformer enameled wire joint is welded at the temperature of 380 ℃.
In some preferred embodiments, the sum of the weight percentages of cobalt and yttrium is < 0.06%.
In some preferred embodiments, the sum of the weight percentages of germanium and cobalt is < 0.06%.
In some preferred embodiments, the sum of the weight percentages of germanium and yttrium is < 0.06%.
In some preferred embodiments, the sum of the weight percentages of germanium, cobalt and yttrium is less than or equal to 0.06%.
In some preferred embodiments, the weight percentage of germanium, cobalt and yttrium is 10 to 30: 3: 4.
in some preferred embodiments, the weight percentage of germanium, cobalt and yttrium is 20: 3: 4.
the inventor finds that the property of tin is stable at normal temperature in the experimental process, but the phenomenon that tin is oxidized often occurs when the tin is used under the high-temperature condition, so that the form and the like of tin are changed, the main reason is that the tin is a tetragonal crystal structure at normal temperature, the crystal lattice of tin is changed along with the temperature rise and the temperature fall, and in order to ensure the application of tin alloy in the welding process of a transformer enameled wire joint, the inventor is researched and found through a large number of creative experiments, germanium, cobalt and yttrium are added into the system, and the weight ratio of the germanium, the cobalt and the yttrium is ensured to be 20: 3: 4, when the sum of the weight percentages of germanium, cobalt and yttrium is less than or equal to 0.06%, the joint welding of the transformer enameled wire can be carried out at the high temperature of 380-430 ℃, and the inventor speculates that the reason of the phenomenon is as follows: cobalt has extremely high temperature resistance, and when the cobalt is compounded with germanium and yttrium for use, the affinity with oxygen can be further enhanced, a stable yttrium oxide or cobalt oxide protective film is formed, oxygen is prevented from diffusing and immersing into the alloy, the oxidation degree of tin in the alloy is slowed down, and the application value of the tin alloy is improved.
In some preferred embodiments, the weight of germanium is 0.8 to 1 wt% of the weight of copper.
In the experimental process, the inventor finds that the content of the added germanium and copper is strictly controlled, when the weight of the germanium is 0.8-1 wt% of the weight of the copper, the phenomenon of tip drawing can be avoided when the pin of the transformer is pulled away from the molten tin liquid level in the tin immersion process, the plating layer of the pin is ensured to be smooth and flat, the appearance consistency of the pin is ensured, and the occurrence of bad phenomena in the welding process and the pollution on the surface of a welding spot are avoided.
The second aspect of the present invention provides a method for preparing a tin alloy, comprising the steps of:
1) preparing materials according to the mass percentage of the raw materials;
2) and (3) mixing the raw materials prepared in the step (1) to obtain a metal mixture, and then melting and homogenizing in a melting furnace to obtain the alloy.
In a third aspect of the invention, an enameled wire is provided, which is made of a tin alloy.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
A tin alloy is prepared from the following raw materials in percentage by weight: 4% of copper, 0.2% of nickel, 0.04% of germanium, 0.006% of cobalt, 0.008% of yttrium and the balance of tin.
A preparation method of tin alloy comprises the following steps:
1) preparing materials according to the mass percentage of the raw materials;
2) and (3) mixing the raw materials prepared in the step (1) to obtain a metal mixture, and then melting and homogenizing in a melting furnace to obtain the alloy.
Example 2
A tin alloy is prepared from the following raw materials in percentage by weight: 4.5% of copper, 0.2% of nickel, 0.04% of germanium, 0.006% of cobalt, 0.008% of yttrium and the balance of tin.
The tin alloy was prepared according to example 1.
Example 3
A tin alloy is prepared from the following raw materials in percentage by weight: 5% of copper, 0.2% of nickel, 0.04% of germanium, 0.006% of cobalt, 0.008% of yttrium and the balance of tin.
The tin alloy was prepared according to example 1.
Example 4
A tin alloy is prepared from the following raw materials in percentage by weight: 4.5% of copper, 0.2% of nickel, 0.02% of germanium, 0.006% of cobalt, 0.008% of yttrium and the balance of tin.
The tin alloy was prepared according to example 1.
Example 5
A tin alloy is prepared from the following raw materials in percentage by weight: 4.5% of copper, 0.2% of nickel, 0.006% of germanium, 0.006% of cobalt, 0.008% of yttrium and the balance of tin.
The tin alloy was prepared according to example 1.
Example 6
A tin alloy is prepared from the following raw materials in percentage by weight: 2% of copper, 0.2% of nickel, 0.04% of germanium, 0.006% of cobalt, 0.008% of yttrium and the balance of tin.
The tin alloy was prepared according to example 1.
Example 7
A tin alloy is prepared from the following raw materials in percentage by weight: 6% of copper, 0.2% of nickel, 0.04% of germanium, 0.006% of cobalt, 0.008% of yttrium and the balance of tin.
The tin alloy was prepared according to example 1.
Example 8
A tin alloy is prepared from the following raw materials in percentage by weight: 8% of copper, 0.2% of nickel, 0.04% of germanium, 0.006% of cobalt, 0.008% of yttrium and the balance of tin.
The tin alloy was prepared according to example 1.
Example 9
A tin alloy is prepared from the following raw materials in percentage by weight: 4.5% of copper, 0.2% of nickel, 0.04% of germanium, 0.04% of cobalt, 0.04% of yttrium and the balance of tin.
Example 10
A tin alloy is prepared from the following raw materials in percentage by weight: 4.5% of copper, 0.2% of nickel, 0.006% of cobalt, 0.0008% of yttrium and the balance of tin.
And (3) performance testing:
1. and (3) testing the fluidity: the tin alloy prepared in the embodiment of the application is used for fluidity test, a metal fluidity spiral die is adopted in the test mode, length recording is carried out according to the scale of the tail end of the die, the specified length is more than 500mm, and the fluidity is recorded as excellent; the length is between 100 and 500mm, and the fluidity is marked as good; the length is less than 100mm, and the fluidity is recorded as poor; and the test results are reported in the table below.
2. And (3) copper corrosion resistance test: the tin alloy prepared in the embodiment of the application is used for a copper corrosion resistance test, a copper wire with the wire diameter of 0.1mm is taken and added into a tin alloy liquid formed by the tin alloy prepared in the embodiment at the temperature of 400 ℃, the time for the copper wire to be completely melted and disconnected is recorded, and the test result is recorded in the following table.
3. Appearance change: the tin alloys prepared in the examples were placed in an artificial atmosphere according to GB/T10125-2012 for 1 month, observed for appearance changes and the results are reported in the following table.
Figure BDA0003074391950000061
Figure BDA0003074391950000071
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The tin alloy is characterized by comprising the following preparation raw materials: at least three of copper, tin, germanium, nickel, cobalt and yttrium.
2. The tin alloy of claim 1, wherein the starting materials comprise copper, tin, germanium, cobalt, yttrium.
3. The tin alloy of claim 2, wherein the raw materials for the preparation comprise, in weight percent: 3 to 6 percent of copper, 0.15 to 0.3 percent of nickel, 0.001 to 0.075 percent of germanium, 0.001 to 0.01 percent of cobalt, 0.0005 to 0.005 percent of yttrium, and the balance of tin.
4. The tin alloy of claim 2 or 3, wherein the raw materials for the preparation comprise, in weight percent: 3-5% of copper, 0.18-0.25% of nickel, 0.005-0.05% of germanium, 0.005-0.008% of cobalt, 0.0005-0.001% of yttrium and the balance of tin.
5. Tin alloy according to claim 4, wherein the sum of the percentages by weight of cobalt and yttrium is < 0.06%.
6. Tin alloy according to claim 4, wherein the sum of the percentages by weight of germanium and cobalt is < 0.06%.
7. Tin alloy according to claim 4, wherein the sum of the percentages by weight of germanium and yttrium is < 0.06%.
8. The tin alloy of claim 4, wherein the sum of the weight percentages of Ge, Co, and Y is 0.06% or less.
9. A method for preparing a tin alloy according to any one of claims 1 to 8, comprising the steps of:
1) preparing materials according to the mass percentage of the raw materials;
2) and (3) mixing the raw materials prepared in the step (1) to obtain a metal mixture, and then melting and homogenizing in a melting furnace to obtain the alloy.
10. An enameled wire, characterized in that it is made of a tin alloy according to any one of claims 1-8.
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Citations (9)

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WO2007049025A1 (en) * 2005-10-24 2007-05-03 Alpha Fry Limited Lead-free solder alloy
US20070178007A1 (en) * 2005-12-27 2007-08-02 Kabushiki Kaisha Toshiba Lead-free solder, solder joint product and electronic component
KR100833113B1 (en) * 2007-12-31 2008-06-12 덕산하이메탈(주) Lead free solder alloy and manufacturing method thereof
JP2013049073A (en) * 2011-08-30 2013-03-14 Nihon Almit Co Ltd Solder alloy
US20160084306A1 (en) * 2013-04-15 2016-03-24 Zollern Bhw Gleitlager Gmbh & Co. Kg Tin-based sliding bearing alloy
CN106031963A (en) * 2015-03-11 2016-10-19 中山翰华锡业有限公司 A lead-free and silver-free tin bar and a preparation method thereof
CN107245602A (en) * 2017-06-09 2017-10-13 升贸科技股份有限公司 Lead-free tin alloy and use its tinned wird
CN110900036A (en) * 2012-10-09 2020-03-24 阿尔法组装解决方案公司 High-temperature reliable lead-free and antimony-free tin solder
WO2020135932A1 (en) * 2018-12-27 2020-07-02 Alpha Assembly Solutions Inc. Lead-free solder compositions

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007049025A1 (en) * 2005-10-24 2007-05-03 Alpha Fry Limited Lead-free solder alloy
US20070178007A1 (en) * 2005-12-27 2007-08-02 Kabushiki Kaisha Toshiba Lead-free solder, solder joint product and electronic component
KR100833113B1 (en) * 2007-12-31 2008-06-12 덕산하이메탈(주) Lead free solder alloy and manufacturing method thereof
JP2013049073A (en) * 2011-08-30 2013-03-14 Nihon Almit Co Ltd Solder alloy
CN110900036A (en) * 2012-10-09 2020-03-24 阿尔法组装解决方案公司 High-temperature reliable lead-free and antimony-free tin solder
US20160084306A1 (en) * 2013-04-15 2016-03-24 Zollern Bhw Gleitlager Gmbh & Co. Kg Tin-based sliding bearing alloy
CN106031963A (en) * 2015-03-11 2016-10-19 中山翰华锡业有限公司 A lead-free and silver-free tin bar and a preparation method thereof
CN107245602A (en) * 2017-06-09 2017-10-13 升贸科技股份有限公司 Lead-free tin alloy and use its tinned wird
WO2020135932A1 (en) * 2018-12-27 2020-07-02 Alpha Assembly Solutions Inc. Lead-free solder compositions
TW202031908A (en) * 2018-12-27 2020-09-01 美商阿爾發金屬化工公司 Lead-free solder compositions

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